Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
  • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
  • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
  • C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/904—Artificial leather
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]

Definitions

• This invention relates to aqueous organic solvent-dispersible thermoplastic polyurethanes.
• the invention particularly relates to aqueous alcohol-dispersible polyurethanes having hydrophilic and hydrophobic segments.
• U.S. Patent Nos. 3,905,929 and 3,920,598 disclose water-dispersible polyurethanes having side chain polyoxyethylene units
• U.S. Patent Nos. 4,028,313 and 4,092,286 disclose water-dispersible polyurethanes having both an ionic salt-type group and side chain polyoxyethylene units.
• U.S. Patent No. 4,110,284 discloses the preparation of ionic group-containing polyurethane latexes by the reaction of a hydrophilic polyester or polyether with an organic polyisocyanate. The patent does not disclose polyurethanes that can be coated onto a substrate and subsequently redispersed in water or aqueous organic solvents.
• linear polyurethanes of my invention can be used as protective coatings, primers, binders, etc.
• thermoplastic organic polyurethane resins having excellent adhesion to substrates and a process for the production of such polyurethanes.
• the polyurethanes of the invention have hydrophilic and hydrophobic segments and the general formula: wherein a, b, c, and d are numbers expressing the mole ratios of polyurethane hydrophilic, connecting, hydrophobic and chain extending segments within the respective parentheses in which a is 1, c is 0.1 to 20, d is 0 to 20, and b is (a + c + d);
• the redispersible polyurethane resins of the invention are prepared by reaction of hydrophilic diols, hydrophobic diols, diisocyanates, and, optionally, chain extenders.
• Suitable hydrophilic diols for providing hydrophilic segments of the polyurethanes are bis(w-hydroxy- aliphatic) esters of sulfo-substituted dicarboxylic acids. They are prepared by the esterification of a diol having a molecular weight of 150 to 3500, preferably between about 500 and 2000, with a dicarboxylic acid, lower alkyl ester, halide, or anhydride that has a sulfo group substitution.
• sulfo group is meant a -S0 3 X group in which X is hydrogen, an alkali metal cation, such as sodium, potassium, and lithium; an alkaline earth metal cation, such as magnesium, calcium, and barium; and primary, secondary, tertiary, and quaternary ammonium cations having one to 18 carbon atoms, such as ammonium, methylammonium, butylammonium, diethylammonium, triethylammonium, tetraethylammonium, and benzyltrimethylammonium.
• X is monovalent.
• Suitable sulfo-substituted dicarboxylic acids for preparation of these hydrophilic diols include: sulfoalkanedicarboxylic acids such as sulfosuccinic acid, 2-sulfoglutaric acid, 3-sulfoglutaric acid and 2-sulfododecandioic acid; sulfoarenedicarboxylic acids such as 5-sulfoiosphthalic acid, 2-sulfoterephthalic acid, 5-sulfonaphthalene-1,4-dicarboxylic acid; sulfobenzylmalonic acids such as those described in U.S. Patent No.
• Diols suitable for condensation with the aforementioned sulfo-substituted dicarboxylic acid in preparing the hydrophilic diol are the polyoxyalkylene diols, polyesterdiols, and polylactonediols having a number average molecular weight of about 150 to 3500.
• Diols having a molecular weight less than about 150 do not confer sufficient organic character to the hydrophilic segment for it to be sufficiently soluble or compatible with other components for efficient reaction in the polyurethane preparation.
• a molecular weight about 3500 reduces the hydrophilizing action of the sulfo group causing reduced dispersibility of the polyurethane of the invention in aqueous solvents.
• Preferred diols have a molecular weight of from about 500 to about 2000.
• Suitable diols also should be free of active hydrogens (other than the hydrogens present in the hydroxy groups) as can be determined by the method described in Zerewitinoff, J. Am. Chem. Soc. 49, 3183 (1927).
• Exemplary diols include polyoxyalkylenediols, such as and and polyesterdiols, such as and wherein
• polyoxyalkylenediols include polyoxyethylenediol, polyoxypropylenediol, and polyoxy- butylenediol.
• Useful commercially available polyoxyalkylenediols include the polyoxytetramethylenediols available from Quaker Oats Company as "Polymeg” 650 and 1000; the polyoxyethylenediols available from Union Carbide as "Carbowax" 400 and 600; and the poly(oxyethylene-oxypropylene) glycols available as "Pluronics" from Union Carbide.
• Polyesterdiols suitable for use in preparing the hydrophilic segment precursor diol and exemplified above are also well known in condensation polymer art. They are generally prepared by the condensation of one or more diols such, as, for example, neopentyl glycol, propylene glycol, and dipropylene glycol with one or more dicarboxylic acids, such as, for example, succinic acid, butenedioic acid, adipic acid, maleic acid, plutaric acid, suberic acid, isophthalic acid, and 1,4-cyclohexane dicarboxylic acid.
• dicarboxylic acids such as, for example, succinic acid, butenedioic acid, adipic acid, maleic acid, plutaric acid, suberic acid, isophthalic acid, and 1,4-cyclohexane dicarboxylic acid.
• Other polyesterdiols are those obtained from the condensation of hydroxyalkanoic acids, such as, for example,
• polyesterdiols are those prepared by polymerizing one or more substituted or unsubstituted lactones, particularly caprolactone using a diol or dicarboxylic acid as an initiator as is described in U.S. Patent Nos. 3,169,945 and 3,700,643.
• Suitable commercially available polyesterdiols for use in preparing the hydrophilic segment precursor diol include poly(ethyleneadipate)diols available from Mobay Chemical Company as "Multron” R series diols such as R-2, R-12A and R-16 and the aliphatic polyesterdiol "Paraplex U-148" available from Rohm and Haas.
• Particularly suitable commercial diols are the polycaprolactone diols available from Union Carbide as the "PCP" series diols such as "PCP" 0200 and 0230.
• the hydrophilic polyol is prepared by an esterification reaction of a sulfo-substituted dicarboxylic acid or its lower alkyl ester, halide or anhydride with a diol as described above.
• the esterification reaction is carried out by heating the acid or derivative with about two mole equivalents of diol and about 0.5 to 5 percent by weight, based on the acid, of a catalyst such as toluene-sulfonic acid, tertiary amines, titanium esters, and the like, as is well known in the esterification art.
• the mixture is heated to 150 to 250°C and held at this temperature until the reaction is complete, generally less than about ten hours, as can be determined spectrometrically or by measurement of evolved alkanol (that is, when a lower alkyl ester of a sulfo-substituted dicarboxylic acid, the preferred derivative, is used).
• the reaction is performed under an inert atmosphere, i.e., nitrogen. It is also desirable to employ a reduced pressure on the reactants during the last 5 to 30 minutes of the heating period.
• Suitable diisocyanates for use as the connecting segment are any of the aliphatic, aromatic and heterocyclic diisocyanates known in the polyurethane field.
• preferred diisocyanates include 2,4-tolylene diisocyanate, 3,5,5-trimethyl-l-isocyanato-3-isocyanato- methylcyclohexane (also called isophorone diisocyanate and sold under the trademark "IPDI” by Veba-Chemie AG), methylene bis-(4-cyclohexylisocyanate) sold under the trademark "Hylene” WS by duPont, hexamethylene diisocyanate, and 1,3-di(isocyanatoethyl)hydantoin.
• Other suitable diisocyanates are described in U.S. Patent Nos. 3,641,199; 3,700,643; and 3,931,117, among many others.
• Hydrophobic diols from which the hydrophobic segments of the polyurethanes of the invention can be derived are in the same generic families of diols suitable for use in the hydrophilic diols of the invention with the exclusion of polyoxyethyleneglycols.
• Suitable hydrophobic diols should have a number average molecular weight of about 400 to 4000, and preferably from about 500 to about 2000.
• the influence of the hydrophilic segment increases so that at molecular weights below about 400, the polyurethanes become water soluble.
• the influence of the hydrophilic segment decreases so that as molecular weights of the hydrophobic diol are increased above about 4000, the polyurethane becomes less and less dispersible in aqueous organic solvents.
• hydrophobic diols include polyoxyalkylenediols, such as and and polyesterdiols, such as and wherein
• PECH diols hydroxyl- terminated poly(haloalkyleneether)s
• a haloaliphatic epoxide for brevity, called a Lewis acid-type catalyst in accordance with methods such as are described in U.S. Patent No. 2,581,464.
• Hydrophobic diols are prepared by processes similar to those employed for the preparation of the hydrophilic diol with the exception that sulfo-substituted dicarboxylic acids are not employed and the use of a reaction catalyst is not always necessary.
• Chain extenders that can be used in the linear redispersible polyurethanes of the invention are well known in the art and include any compound having two active hydrogen-containing groups and a molecular weight between 18 and about 200. Suitable compounds include water, diols, amines, bis(monoalkylamine) compounds, dihydrazides, dithiols, N-alkylaminoalkanols, hydroxy- alkylthiols, hydroxyalkanoic acids, thioalkanoic acid and the like.
• Preferred chain extenders are the diols having the formula HO(CH 2 ) e 0H in which e is 2 to 12, glycols of the formula HO( ⁇ CH 2 CH 2 O) ⁇ f H in which f is 1 to 6, glycols of the formula HOfCH(CH 3 )CH 2 )]gH in which g is 1 to 4, e.g., ethylene glycol, propylene glycol, diethylene glycol, diisopropylene glycol, and the like, 2,2-dimethyl-l,3-propanediol, 2,2-diethyl-1,3-propanediol, 3-methyl-1,5-pentanediol,1,4-cyclohexandiol, 1,4-(dihydroxymethyl)cyclohexane and the like.
• terminal groups in the polyurethanes of the invention is relatively unimportant and certainly difficult to ascertain by analysis, there being only two such terminal groups per molecular weight of about 500 to 40,000 or more. It is postulated that where an excess of hydroxyl equivalency over isocyanate equivalency is used in the polyurethane, A in formula I is hydroxyl. Where an excess of isocyanate equivalency over hydroxyl equivalency is used, A is isocyanate. The presence of trace impurities having active hydrogens (i.e., a monohydric alcohol such as methanol would probably cause A to become methyl) would alter the isocyanate group depending on the nature of the impurity.
• trace impurities having active hydrogens i.e., a monohydric alcohol such as methanol would probably cause A to become methyl
• the redispersible polyurethane resins of my invention are prepared by the co-reaction of diisocyanate with hydrophilic diol, hydrophobic diol, and where used, chain-extenders under essentially anhydrous conditions. Components are maintained essentially anhydrous during their preparation or are dried as a first stage during their preparation by a suitable technique such as the distillation of a water azeotroping solvent, e.g., benzene or toluene.
• a suitable technique such as the distillation of a water azeotroping solvent, e.g., benzene or toluene.
• the reaction can be carried out using a reactor equipped with agitator, means for heating and cooling, means for maintaining a dry atmosphere (flooding with dry nitrogen is satisfactory), means for adding components, and means for withdrawing reaction products.
• hydrophilic diol Into the reactor is charged (on a molar basis) one mole of hydrophilic diol, about an equal weight of an inert organic solvent, e.g., methyl ethyl ketone, methyl isobutyl ketone, benzene, tetrahydrofuran, ethylene- chloride or the like, and about 0.01 to 1 percent by weight of a urethane polymerization catalyst, such as stannous octoate.
• the mixture is agitated and heated to a temperature between 25 to 100°C, preferably between about 40 to 70°C and then b moles of diisocyanate are added over a period of about 0.5 to 3 hours while maintaining the temperature, preferably, between about 40 to 70°C.
• the reactants are heated for about an additional hour after which c moles of hydrophobic diol are added. Heating is continued for about an hour and then, if it is to be used, d moles of chain-extending diol are added over a period of about 0.5 hours. Additional heat is then applied to raise the agitating contents to a temperature between about 75 to 100°C (the refluxing temperature of the solvent). Heating at this temperature is continued until infrared spectrometric analysis of a sample of the reactants indicates depletion of isocyanate. The content of the reactor is then discharged from the reactor. The solution of aqueous organic solvent-dispersible polyurethane is then ready for use in various applications. Solvent can be removed, if desired, by drum drying or similar procedures known in the art or additional solvent and/or other adjuvants added in accordance with the particular use to be made of the polyurethane.
• Adjuvants which can be added to the redispersible polymers of the invention to modify their characteristics include one or more of various materials such as plasticizers, dyes, pigments, organic and inorganic fillers, fire retardant agents, antioxidants, ultraviolet stabilizers, optical brighteners, and the like. Generally, depending on the desired modification, from about 1 to 50 percent by weight of the adjuvants can be added.
• the redispersible polyurethanes are useful as protective coatings that can be readily removed by water or an aqueous solvent; as a primer for providing adhesion of a hydrophilic layer, e.g., a photographic emulsion, to a hydrophobic layer, e.g., a polyester film, etc.
• the polyurethane obtained had an intrinsic viscosity of 0.36 in dimethylformamide and a glass transition temperature, Tg, of -2°C.
• the polymer was soluble in neither water nor isopropanol, but readily soluble in 40/60 isopropanol/water mixtures. Films cast from a 10 percent by weight solution of the polyurethane were tough and clear and could be redispersed in isopropanol/water.
• hydrophilic diols were prepared in accordance with the procedure given in Part A of Example C using in place of PCP 0200 polycaprolactone, the reactants and amounts shown in Table I. The molecular weight measured for each of the hydrophilic diols obtained is given in the table.
• aqueous organic solvent-redispersible polyurethanes were prepared in accordance with the general procedure given in Example 1 using the various component hydrophilic diols, hydrophobic diols, diisocyanates, and when used, chain-extenders listed.
• the polyurethane obtained had an intrinsic viscosity of 0.32 in dimethylformamide and a T g of -32°C. Dried films were readily dispersed in isopropanol/water.
• the polyurethane obtained had an intrinsic viscosity of 0.39 in dimethylformamide, a T g of -55°C, and a Tm of 41°C. Dried films were readily dispersed in 50 percent by volume isopropanol in water.
• the polyurethane obtained had an intrinsic viscosity of 0.37 in dimethylformamide and a Tg of -28°C. Dried films were readily dispersed in 50 percent by volume isopropanol/water.
• the polyurethane obtained had an intrinsic viscosity of 0.41 in dimethylformamide and a T of. -3°C. Dried films were readily dispersed in 40/60 by volume isopropanol/water.
• Example 13 was repeated using as a chain extender an equivalent amount of water in place of the ethyleneglycol.
• the polyurethane obtained had an intrinsic viscosity of 0.39 in dimethylformamide and a T g of -7°C. Dried films were readily dispersed in 50 percent by volume isopropanol/water.
• Example 13 was repeated using as a chain extender 2.9 g (0.025 mole) of 1,6-hexamethylenediamine. An intrinsic viscosity of 0.40 and a T g of -42°C were measured.
• the polyurethane obtained had an intrinsic viscosity of .32 in dimethylformamide and a T g of 20°C. Dried films were readily dispersed in 50 percent by volume isopropanol/water.
• the polyurethane obtained had an intrinsic viscosity of .39 in dimethylformamide and a T g of -18°C. Dried films were readily dispersed in 50 percent by volume isopropanol/water.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)

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• 1980
  • 1980-04-30 US US06/145,026 patent/US4307219A/en not_active Expired - Lifetime
• 1981
  • 1981-04-10 DE DE8181301601T patent/DE3175629D1/de not_active Expired
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